Cyclic hydrocarbon and process for preparing the same



Patented Sept. 30, 193() UNITED STATES PATENT OFFICE- OTTO NICODEMUS AND WALTER BERNDT,

TION OF DELAWARE or Hocrrs' oN-rnE-unn, GER-MANY, Ai- SIGNORS r01 GENERAL ANILINE worms, me, or new YORK, N. Y., A, coaroaa- CYOLIG HYDROCABIBON AND PROCESS FOR PREPARING THE SAME 80 Drawing. Application filed April 20, 1926, Serial No. 103,357, and in Germany April 24, 1925.

The present-invention relates to a process 7 of preparing cyclic compounds and to new 4 products obtainable thereby.

\Ve have found that when the vapors of 5 certain compounds are conducted at an elevated temperature over highly-porous bodies,

suchas highly-active charcoal, silica-gel or alumina-gel, new cyclic systems are formed with a good yield and in a continuous and technically rapid way. Theoompounds to be used as starting materials in our process possess the atom gropping:

carbon atom marked C contains a hydrogen atom attached to it, and Y represents hydrogen, chlorine, or a hydrocarbon residue. For example, they may be ketones possessing the -m rou' in: ato pig p g as in the above formula, or they may be carbinols possessing the atom grouping:

I v l or methane derivatives and so on.

carbon atom which is in ,B-position to the such" as,

" vided that all these ketones contain a met yl- It is advantageous to operate in presence of oxidizing media, which can only be omitted,.if ketones are utilized for the formation of the cyclic chains. When using other starting materials .the presence of oxygen is necessary and for this purpose there are added to the highly-active substances some further suitable catalyzers which, like iron oxides, manganese oxides, cobalt oxides, vanadium oxides, act as catalytic oxygen carriers.

Thus there may be preparedby our new process for instance ,B-methylanthracene from benzoyl-m-x'ylene in a continuous way with a goodyield and in excellent purity.

The reaction takes place according to the following scheme:

0 on; on.

Furthermore, by using difierent ketones, a great variety of hydrocarbons related to anthracene. can be obtained. 1

Thus, the ketones may be of symmetric or asymmetric structure, representing derivatime or substitution products of ,benzophenone or also of polynucleararomatic ketones (nagihthalene). Likewise di-ketones,

or instance,- isophthaloxyl-xylene, arecapable of forming closed chains roor methylene group in 'ortho positionto the carbony group.

However, the reaction is not restricted to the formation of hexagonal rings, but the use of mixed aliphatic-aromatic ketones also permits the formation of'pentagonal rings.

If, for instance,.the. vapours of aceto-m-xylene are conducted over heated highly-active charcoal, methylinden is obtained with elimination of water, this being a body which was" heretofore not known in a pure state. A0-

cordingto the character of the ketones used,

porous bodies some further .catalytically act-' ing substances. In some cases it may also it may be advantageous to add tothe highlyi be advantageous to work under reduced or increased pressure.

We have found that furthermore all secondary and tertiary aromatic or mixed alcohols, containing a methylor methylene group in ortho position to the carbinol grouf), are capable of forming cyclic chains. n this connection it has been observed that secondary reactions which are caused-by the reducing action of the hydrogen produced during the operation are advantageously avoided by conducting the alcohol vapours, mixed withoxygenfor instance with air-- or with oxygen-yielding agents, such as nitro bodies, over the highly-porous bodies to which, if desired,'some further oxygen carrying catalyzers may be added. For instance: V

O cn V 0H, cm on cn.

The closing of the chaintakes lace in this case with simultaneous formation of 2 mol. of Water and it is immaterial whether the alcohol group is free or etherified or esterified. In every case, the formation of the ring takes place with elimination of the ether group or ester group in form of alcohol or an acid, provided, of course, that an ortho-position to the alcohol group is free which renders possible the formation of the cyclic chain.

y We have moreover found that it is not necessary to start from ketones or alcohols containing a methyl grou in ortho position, but that the dior triary methanes containing a met-hyl or methylene group in ortho position are capable of reactin in the same manner. Also in-this case t e reaction in question can be generally applied including the 'derivatives.and substitution products.

Ascontact substances may be used the highlyporous bodies above, referred to; it is on y preferable to work in presence of an oxidizmg medium and, if .required, to add some {gather oxygen carrier to the highly-porous les.

CaHs

The reaction takes place according to the schemee CH: C (I O T (I o on 0 Furthermore we found that the new process can as well be applied to heterocyclic compounds. It is thus possible to produce cyclic compounds which were mostly hitherto unknown and some of which possess particularly valuable properties owing to their heterocyclic character. For preparing them, there are used such heterocyclic ketones, carbinoles or methane derivatives, as contain a methylor methylene group in ortho-position to the ketone-carbmolor methylene group. The formation of the ring is, in case of need, effected in presence of oxygen or air by the act-ion of the contact substances above referred to, among which the active charcoal has proved to be particularly suitable for the purpose. Also in the. present case the reactionoccurs with elimination of water, for instance according to the equation:

I) (1* 10 on N c CIHl 1h ing material is converted into",B-methylanthracene M. P. 201 C., the unaltered. xylylphenylmethane being returned to the reaction vessel.

(2) Over a contact-substance consisting of highly active charcoal (activated with-phos phoric acid) and charged with co percobaltic oxide, areconducted at 400 the CHOH CH (CHI I 2 H1O CH CH C l C I (3) 'Ortho toluyl-5-acenaphthene is reduced and the carbinol, which melts at 145 C HI C. and dissolves in sulfuric acid with an separates as light yellow leaflets which melt at 191 C. and dissolve in sulfuric acid with a reddish violet color of a strong fluorescence. ,The, closing of the ring occurs according to the following scheme:

CHrCHt CHPCH! The yield amounts to 35% of the theory. The

unaltered parentmaterial is returned to the contact furnace. Analysis of the above mentioned anthracene showed rum 0. 5.78% 121.

. against 94.4 C. 6.6 73 H. as previously calculated.

(4) Over a catalyst, consisting of highly active charcoaliheated to 400 C are conducted the vapours of m-xylenecarbinol-acetate mixed with airduring which operation the ester effects the closing of the ring to form the B-methylanthracene with elimination of "acetic acid and water. By recrystallizing the reaction product from glacial acetic acid the fl-m'ethylanthracene is obtained in a pure he product of the reaction state and with a yield of 30%, the mother liquors containin benzoyl-m-x lene in the amount of 50% o the ester emp oyed.

(5) Into a copper contact-pipe, charged with 600 ccmpof active charcoal-obtained from so-called crude-coke by activation with water-vapour-, benzoyl-m-xylene is introduced at 380-400 C. drop by drop in such a manner that in the course of an hour 100 g. of the benzoyl-m-xylene pass the catalyst. The vapours emanating from the pipe become condensed into a crystal cake and water. After having drawn ofi the water there is obtained fromcl270 g. of the ketone used 1090 g. of a crystal cake which constitutes a mixture of B methylan thracene and unaltered ketonea By squeezing the cake, 500 g. of benzo l-m-xylene are recovered, which are immediately returned into the contact pipe. press are mixed and stirred for a short time with alcohol or benzol, again pressed off and they yield 540 g. of ,B-methylanthracene of melting point 201 C. The reaction proceeds very easily and the contact cylinder employed remains active for a long time, provided that the ketone contains no substances splitting ofi'.

acids. The ,B-methylanthracene can'be easily converted in the usual manner by oxidation with nitrosyl-sulfuric acid into the corresponding ,B-methylanthraquinone.

(6) Over silica-gel, which has been heated in a pipe made of quartz to 420 C., va pours of ortho-toluyLnaphthalene are conducted. The vapours emanating from the catalyst become condensed into a sublimate showing a beautiful yellow-green fluorescence. which is freed from the admixed arent material by recrystallization from g acial acetic acid. Thus,v 1,2-benzanthracene of melting point 167 C. is obtained from which its picrate, meltingat 132 C., can bev easily prepared.

- The yield of the product is good and the con tact substance remains efiicacious for a conslderable tlme. The reaction occurs accordmg to the equation (7) Q-methyliiaphthenone, of I melting Q point 230-235 C. repared by the action of -a-naphthoic acid 0 loride upon B-methylnaphthalene-is slowly distilled at a pressure of about 5 mm. through a contact (of the kind described in Example 5) at 400 C. while simultaneously evacuating the apparatus. The product of the reaction solidifies in a receiver placed at the rear part of the contact furnace into a yellow crystal cake, which, besides unaltered parent-material, contains dinaphthanthracene'in the amount of 50% of The crystals remaining in the filterthe ketone used. By recrystallization from benzol, the dinaphthanthracene is obtained in apure state in the form of greenish-yellow laminae of melting point 250 C., whereas its picratewhich crystallizes in brownishorange needles*-melts at 210 C. It must be assumed that reaction takes place according to the following scheme and that there fore the constitution of the dinaphthanthracontact. The product of the reaction forms a white crystal cake which constitutes a mixture of unaltered parent material with 2- methylanthracene and 2-chloro-7-methylanthracene. By repeated recrystallization from nitro-benzene the 2-chloro-7-methylanthracene of melting point 270 C. is obtained. The reaction proceeds according to the equation:

CO CH Cl CH1 CH3 Cl CH CH:

cene is the following:

(8) 2-xylyl-5-xyloyl-pyridine is evaporated in vacuo m a weak current of air and then conducted over active charcoal heated to 400 to 420 C. The receiver contains a mixture of the compound of the following formula:

(M. P. 172'": C.)

mo \CH;

' besides unaltered parent material and other is evaporated and con by-products. The former is obtained by recrystallization from methyl alcohol or petroleum ether in a pure state.

(9) Ortho-toluyldiphenylene sulfide, obtained by subjecting diphenylenesulfide to reaction with ortho-tolu l chloride and A101 diicted, under ordinary or reduced ressure, at 400-U C. over high- -porous c arcoal. The closin of the ring is thereby eflected very easily. econdensate is a solid mass, which when treated with cold other, is separated into the unaltered ketone, which is dissolved in the ether whereas the yellowish green anthracene derivative remains. The yield is up to Recrystallized from glacial acetic acid it constitutes a yellow body showing a which melts at 249-250 violet color. to the following equation:

cinema (10) p-chlorbenzoyl-m-xylene is distilled over a contact (of the kind described in Example 3) at 400 C. while evacuating the apparatus in such a manner that in the course of an hour 80-100 g. of the material passes the The reaction occurs according n fluorescence Its solution in concentrated sulfuric acid has a reddish-v \Ve claim:

1. The rocess which comprises conducting over highly-porous bodies having highly active properties and the property of extensively absorbing 'gases and vapors, at an elevated temperature sufiicient to cause a ring-closing but below a carbonizing temperature, the vapors of a compound possessing the atom grouping:

wherein C and C represent carbon atoms belonging to an aromatic or heterocyclic nucleus, X represents an ali hatic, aromatic, or heterocyclic residue, in'gw ich at least one carbon atom which is in B-position to the carbon atom marked G, contains a hydro-.

gen atom attached to it, and Y re resents hydrogen, chlorine or a hydrocar n residue.

2. The rocess which com-prises conducting over highly-porous bodies having highly active r0 ert-ies and the property of extensive y a orbing gases and vapors, at an elevated teln rature suflicient to cause a ring-closin ut below a carbonizing temrature, t e vapors of a compound possessmg the atom grouping:

closing but below a carbonizing temperature, the vapors of a compound possessing the atom grouping:

wherein C and C represent carbon atoms belonging( to an aromatic or heterocyclic nucleus, represents an aliphatic, aromatic,

or heterocyclic residue in which at least one carbon atom which is in ,B-position to the carbon atom marked C contains a hydroen atom attached to it, and Y, represents ydrogen, chlorine, or a hydrocarbon residue.

over hig 4. The }process which comprises conducting ly-porous bodies having highly rties and the property of extensivel a sorbing gases and vapors, at an elevate tem erature sufiicient to cause a ring-closin perature, t e vapors of a compound possessing the atom grouping:

active pro y it. 6 \x a o E f i 1 H- \CH:

whereinC and C represent carbon atoms belongin to a nucleus of the group including the nzene and na hthalene series and C and C represent car 11 atoms belonging to an aromatic or heterocyclic nucleus.

6. The process which comprises conducting over highly-porous bodies having highly active properties and the property of extensive-' ly absorbing gases and vapors, at an elevated ut below a carbonizing temtemperature sufiicient to cause a ring-closing but below a carbonizin temperature, the va ors of a compound hav ng the general formu a:

wherein X represents hydrogen or a monovalent substituent. v v

7. The process which comprises conducting over highly porous bodies having highly active pro erties and the property of extensively a sorbing gases and vapors, at a temperature between about, 320 C. and about 450 C., the vapors of a compound possessing the atom grouping:

wherein C1 and C represent carbon atoms belonging( to an aromatic or heterocyclic nucleus, represents an aliphatic, aromatic, or heterocyclic residue, in which at least one carbon atom which is in B-position to the carbon atom marked C contains a hydrogen atom attached to it, and Y represents hydrogen, chlorine or, a hydrocarbon residue. 1

8. The process which comprises conduct-in g over highly porous bodies having highly active properties and the property of extensively absorbing gases andvapors, at a temperature between about 320 C. and about 450 C., the vapors of a compound possessing the atom grouping: v

wherein C1 and C represent carbon atoms belonging to an aromatic or heterocyclic nucleus and X represents an aliphatic, aromatic, or heterocyclic residue in which at least one carbon atom which'is in B-position to the carbon atomsmarked C contains a hydrogen atom attached to it. p

9. The process which comprises conducting over highly porous bodies having highly active properties and the property of extensively absorbing gases and vapors, at a temperature'between about 320 C. and about 450 (3., the vapors of a compound possessing the atom grouping:

1 Y) 0 3 1o iv at least one h is in ,B-position to the C contaans a hydrogen Bil H l u l i H m NIH of compounds of the formula:

450 (3., the vapors of a compound having the general formula:

x E X V x m X H X wherein X-represents hydrogen or a mono- 75 valent substituent.

13. As new products, cyclic compounds which are produced by closing the ring mil CERTIFICATE or CORRECTION.

Patent No. 1,776, 924. Granted September 30, 1930, to

orro NICODEMUS ET AL. I

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, line 38, claim 4, strike out the word "hydrocarbon"; and. that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 9th day of December, A. D. 1930.

. g M. J. Moore, (Seal) v Acting Commissioner of Patents;

Certificate of Correction Patent No. 1,776,924. Granted September 30, 1930, to

OTTO NIOODEMUS ET AL.

It is hereby'certified that error appears in the printed specification of the abovenumbered patent requiring. correction as follows: Page 3, between lines38 and 50,

strike out the right-hand formula and insert instead 7 and that the said Letters Patent should be read with this eoi-i-ecmmte l the g same may conform to the record of the case in the Patent'Oifice.

Signed and sealed this 3d day oi February, A. I). 1.331.

' [SEAL] M. J. MOORE,

Acting Comim'ssz'oner of Patents. 

